Radiative Transitions between

Electronic States

November 14, 2002.

Michelle
 4.1 “Paradigm” Shifts
•Maxwell  light as electromagnetic waves

Blackbody Radiation Photoelectric Effect

Wavelength dependence of energy Wavelength dependence of energy
distribution of light emitted by a of electrons emitted when light
hot object strikes a metal

Planck Einstein
Quantization of energy E = h Photons - quantized light
consisting of particles
possessing “bundles” of energy
• DeBroglie  light as a particle with wave properties

E = h = h(c/) = pc
From the perspective of absorption and emission it is
more convenient to think of light in terms of an
oscillating electromagnetic wave 2
 4.2-4.3 Absorption and Emission
Transitions between electronic energy levels accompanied
by absorption or emission of light

Photochemical region of the spectrum: 200-700 nm 143 kcal mol-1-41 kcal mol-1
valence orbital (, , n)  antibonding orbital (*, *)

Chromophore: atom or group acting as a light absorber

Lumophore: atom or group acting as a light emitter
C=O C=C C=C-C=C C=C-C=O aromatics
Molar absorptivity  measures “absorption strength”
units cm-1M-1 NOT cm2mol-1
3
 4.4 The Nature of Light
The classical theory of light is a convenient starting point providing a
pictorial and understandable physical representation of the interaction of
light and molecules
classical theory can be improved by applying quantum interpretations of basic
concepts (orbital, quantized energy etc.)

Dipoles as a model for interactions between electrons and light

oscillating electric dipole field of the electromagnetic wave

oscillating dipoles due to electrons moving in orbitals

 Dipole-dipole interactions are through space and don’t require orbital overlap
(Interactions requiring overlap are “exchange interactions”)

Exciton migration:
Examples electron-hole
of dipolar interactions: pair hopping
London from
dispersion molecule
forces, to
EPR, NMR,
large splittings
molecule for crystals (exciton interactions)
in a crystal 4
 4.4 Dispersion Forces

Correlation of fluctuations in electronic charge distributions in

molecules
•Dipole on A drives
formation of dipole on
B and vice versa
•Fluctuating dipoles are
E ~ ABR-3AB in “resonance”

Energy of the dipole-dipole True for all dipole-dipole

interaction falls off as A and B interactions, magnetic or
move apart, given by R-6AB electric
5
4.4 Light as an Oscillating Electric Field
Frequency () of oscillating field must “match” a possible
electronic oscillation frequency (conservation of energy)
There must be an interaction or coupling between the field
(oscillating dipoles) and the electron
Interaction strength depends on field dipole and induced dipole
strength as well as distance between the two.
Laws of conservation of angular momentum must be obeyed
(electrons, nuclei, spins)
Spin change is highly resisted in absorption due to time
constraints
*the most important interaction between the electromagnetic
field and the electrons of a molecule can be modeled as the
interaction of 2 oscillating dipole systems that behave as
reciprocal energy-donor, energy-acceptors 6
 4.4 Light as an Oscillating Electric Field
 electric
If the field can couple field
to the electrons it can
exchange energy by
driving the system Direction of propogation
into resonance at a H magnetic field
frequency common to
both A light wave generates a
time-dependent force field F

absorption: photons being removed from the

electromagnetic field
ABSORPTION
(reverse for emission) emission: photons being added (?) to the
electromagnetic field
7
4.4 Light as an Oscillating Electric Field
• Radiativetransitions between states are induced by
perturbations which make the two states”look alike” by
inducing a resonance
• Resonancerequires that the two states have the same energy and
momentum characteristics and a common frequency for
resonance
E = h
Energy difference Frequency of light wave
between two states oscillation

The energy of the photon must exactly match the

the energy level difference in the molecule
8
4.4 Light as an Oscillating Electric Field
Force on an electron in a molecue by a light wave
F = e + e[H v]
c

Electrical force
Magnetic force

c >> velectron

Force on an electron
F ~ e

•Major force on electrons is due to the oscillating electric field of

the light wave
•Net
effect of the interaction is generation of a transitory dipole
9
moment in the molecule
4.4 Light as an Oscillating Electric Field

Electric dipole induced by an electric field generated

between two plates
Direction of induced dipole is always parallel to the direction
of the external electric field
10
 4.4 Light as an Oscillating Electric Field
Light and the hydrogen atom
Electric field interaction reshapes
the electron distribution of the 1s
s orbital has 0
units of
orbital
angular
momentum (
h)
p orbital has 1
 photon
must have 1
unit

No node, no vibration  1 node, vibratory motion

Increase in # of nodes essential for absorption and vice versa for emission
11
(related to nodal nature of light “wave”)
4.4 Light as an Oscillating Electric Field

Light and the hydrogen molecule

•Interaction involves  and 

orbitals instead of s and p
•Absorption is    or * and is
analogous to the s  p
transition in the hydrogen atom

12
4.4 Light as a Stream of Particles: Photons
• The
photon as a reagent that may collide and react with
molecules
• Long photons have little energy and momentum, short 
photons have a lot of both
• Largest cross-section of an individual chromophore is ~10 Å
• Nuclei are effectively frozen in space as a photon passes

Spectroscopic Properties and Theoretical Properties

In order to use the laws of quantum mechanics to describe
fundamental properties we have to consider these terms:
f oscillator strength
i transition dipole moment
13
P transition probabilities
 4.4 Oscillator Strength
Probability of light absorption is related to the oscillator strength f
Theoretical Experimental
oscillator strength f ~ 4.3x10 ∫ d
-9
absorption

Strong absorption => f~1 Area under  vs. wavenumber plot

Rate constant for emission k0e is related to  by:

k0e ~ 4.3x10-9 -20 ∫ d ~ -20 f

Oscillator strength can be related to transition dipole moment by:

Transition dipole
moment
f = 8me 2i ~ 10-5|eri|2
f = 8me <H>2
3he2
3he2
Relationship between experimental
14 and
quantum quantities
4.5 The Shape of Absorption and Emission Specta

•Electronictransitions in molecules are not as “pure” as they are in

atoms, in molecules relative nuclei motions must be considered
•An ensemble of nuclear configurations are observed
•“most prominent vibrational progression is associated with the
vibration whose eqm position is most changed by the transition” ?15
4.5 Franck-Condon & Absorption

16
4.5 Franck-Condon & Emission

• The most probable transitions

produce an elongated ground state,
while absorption initiallly produces
a compressed excited state
• In both cases of absorption and
emission, transition occurs from the
=0 level of the initial state to some
vibrational level of the final state 
which level is dependent on the
displacement between  and *
• Band spacing in the resulting
spectrum is determined by the
vibrational structure in the final
state
17
 4.6 State Mixing

State mixing is the first- or higher-order correction to an original zero-

order approximation of single orbital configurations or single spin
multiplicities

Example: an n, * S1 state actually contains a finite amount of , *

character mixed in so the first order wavefunction is given by:
Mixing coefficient
first order (S1) = (n, *) + (, *)
n, *

zero order zero order • Spatial overlap of

Features important to state
n, * , * mixing states
mixing:
• Symmetry properties
• Energy gap between zero  = <a|H|b>
order configurations Ea - E b
• Nature and symmetry
of H
• Magnitude of the matrix
element that mixes the
states < n|H| > = 0 when n and 
are orthogonal 18
4.6 Mechanisms for Mixing Singlet and Triplet

Singlet-triplet transitions are

strictly forbidden in first order
but spin-orbit coupling mixes
singlet and triplet states so
that transitions become
allowed
1. Direct coupling of T1 and Sn
<T1|Hso|Sn> ≠
0
2. Indirect electronic coupling
via and intermediate
triplet state (mixing of T1 with
upper vibrational triplets)
3. Turning on 1. and 2. via
vibrational motions of the19
molecule
4.6 Mechanisms for Mixing Singlet and Triplet

Measurement of “forbidden”
absorptions and emissions
n, * , * provide evidence of the
identity of the mixing state

Vibrational structure
provides clues as to which
motions are most effective in
mixing states

20
 4.7 Molecular Electronic Spectroscopy
Kasha’s Rule: photochemical reactions occur from the lowest excited singlet
or triplet states

• absorption

• emission

• excitation

 ~ [log(I0/It)]/lc Ie = 2.3 I0 AlAe[A]

Optical density for a weakly absorbing solution of A

21
 4.7 Spin-Allowed Transitions
“allowedness” is measured by the oscillator strength f which
can be dissected into:
f = (fe x fv x fs) fmax
fe - electronic factors, fv - Franck-Condon factors, fs - spin-orbit factors

A perfectly allowed transition has f = 1

A spin allowed transition has fs = 1 and for a spin-
forbidden transition fs depends on spin-orbit coupling
fe
Overlap forbiddeness: poor spatial overlap of orbitals
involved in electronic transition
Orbital forbiddeness: wavefunctions which overlap in space
22
but cancel because of symmetry
 4.7 Quantum Yields of Allowed Fluorescence
Quantum yield of emission is given by:
Experimental
e =  k (k + ki) =  k 
0
* e
0
e
-1 0
* e lifetime
Formation efficiency
of the emitting state All rate constants that
deactivate the excited state

ki is very sensitive to experimental conditions:

•Diffusional quenching and thermal chemical reactions may
compete with radiative decay
•Certain molecular motions may also provide competitive
decay pathways
•Measurements at low temperature (77K) cause ki terms to
become small relative to k0e
F = kF(kF + kST)-1 = kF  23
4.7 Quantum Yields of Allowed Fluorescence

Generalizations from experimental observations:

• Rigid aromatic hydrocarbons are measurably fluorescent
• Lowvalue of F for these molecules is usually the result of
competing ISC
• Substitution of H for X generally results in a decrease in F
• Substitutionof C=O for H generally results in a substantial
decrease in F
• Molecular rigidity enhances F

F is an efficiency that compares relative transition probabilities,

24
doesn’t relate directly to rates
4.7 Quantum Yields of Allowed Fluorescence

The highest energy vibrational

band in an emission spectrum
usually corresponds to the 0,0
transition
ET and ES can be obtained
If there is no fine structure the
onset of emission is used to
guess the upper limit of E

25
 4.8 Spin-Orbit Coupling

• Thevalue of (S0T) and k0P(T  S0) are directly related to the

degree of spin-orbit coupling between S0 and T
• S-O coupling depends on:
•Nuclear charge
•Availability of transitions between “orthogonal” orbitals
•Availability of a one atom center transition
• Degree of S-O coupling is related to , a S-O coupling constant
 depends on the orbital configurations involved

26
4.8 Multiplicity Change in Radiative Transitions

Greater oscillator strength than n2  , *

• In general fvfe(, *) > fvfe(n, *)

because (, *) > (n, *) for S-
S transitions where spin is not a
factor
• Implies that fs (n, *) >> fs (, *)
for spin-forbidden radiative
transitions
• a radiative transition n2 *
where the electron jumps from
px to py on the same atom is
very favourable because of the
momentum change
(compensating for the spin
momentum change)
In planar molecules, out of plane vibrations can cause
27
orbital mixing and minor S-O coupling
 4.9 Perturbation of S0T Absorption
Compound possessing lowest energy , * or heavy atoms are usually
insensitive to spin-orbit perturbations
•S T(, *) of aromatics is generally enhanced by S-O perturbation
0

•S T(n, *) of ketones is insensitive to S-O perturbation

0

•S T enhancers
0

•Molecular oxygen
•Organic halides, organometallics
•Heavy atom rare gases

28
 4.9 Perturbation of S0T Absorption

Internal versus external heavy atom effect

Note position dependence

Useful for determining the
nature of the excited state
29
 4.9 Triplet Sublevels

•A triplet state at room temperature is actually a rapidly

equilibrating mixture of 3 states (sublevels Tx Ty Tz)
• Absorption initially produces only one of the three levels
• Normally absorption to the sublevels is not resolved
• Molecules in different sublevels have their electrons in
different planes
• If
T’s are not rapidly equilibrated different phosphorescence
parameters will be observed (above 10K this is usually not
an issue)

30
 4.9 Phosphorescence

 P is not a reliable parameter for characterizing T

 P ~ STk0P(k0P + kTS)-1 gives the quantum yield for
phosphorescence when measured at 77 K and only ISC is
competing
• No reports of phosphorescence from nonaromatic hydrocarbons
•ISCis inefficient for flexible molecules
•T S is spin forbidden AND Franck-Condon forbidden (twisted triplet)
1 0

•Large kd due to surface “touching” between T1 and S0

• Theoretical relationship between P or T and molecular structure
is not direct
• Small P may be due to low ST or to kd>>k0P
• Phosphorescence may be measured at room temperature if:
•Triplet quenching impurities are rigorously excluded 31

• 4 0
4.11 Excited State Structures

S1 and T1 states are

electronic isomers of S0

32
 4.12 Complexes and Exciplexes

• 2 or more molecules may participate in a cooperative

absorption or emission
• Spectroscopic characteristics are:
• Observation of a new absorption band not characteristic of
starting components
• Observation of a new emission band not characteristic of starting
components
• Concentration dependence of the new absorption/emission
intensity

Exciplex or excimer: an excited molecular complex that is dissociated

or only weakly associated in the ground state
33
4.12 Complexes and Exciplexes

Mixtures of molecules
with low IP or high
EA often exhibit
charge-transfer
absorption bands
(EDA bands)

This type of
absorption is very
sensitive to changes in
solvent polarity

Transition from
* can be thought
of as D,AD+ A- 34
 4.12 Complexes and Exciplexes

Energetic considerations Collision between M* and

polarizable ground state N
will usually result in a
complex stablized by some
charge-transfer interactions
if M*N properties are
distinct this is an exciplex
or excimer
Exciplex/mer emission will
occur to a very weakly
bound or dissociative
ground state
Favourable formation is a
balance with entropic
considerations 35
4.12 Complexes and Exciplexes

•Exciplex/excimer emission is
featureless
•Excimer emission is not as
solvent dependent as
exciplex (less charge-transfer
stabilization)
•Intramolecular
exciplexes/eximers are also
possible when the linkage is
of the appropriate length
•Formation of excited state
complexes can also be
monitored by time-resolved
spectroscopy
36
 4.13 Delayed Fluorescence

The observed F may be longer than expected based on

“prompt” emission...

Thermal repopulation Triplet-triplet

of S1 anihilation
When the S-T gap is Combination of 2
small and the ISC is triplets to form a
fast the S1 state can be sinlget state from
repopulated from Tn which emission is
observed
Effect disappears at
low temperatures Es  ET + ET
37
4.14 The Azulene Anomaly

Emission from upper

excited states

Large S2-S1 gap slows

down the interconversion
which would normally
cause all emission to be
from S1

38